CN106925342A - Modified form H-G hydrocracking catalyst and preparation method thereof - Google Patents
Modified form H-G hydrocracking catalyst and preparation method thereof Download PDFInfo
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- CN106925342A CN106925342A CN201710264308.0A CN201710264308A CN106925342A CN 106925342 A CN106925342 A CN 106925342A CN 201710264308 A CN201710264308 A CN 201710264308A CN 106925342 A CN106925342 A CN 106925342A
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- molecular sieve
- modified form
- hydrocracking catalyst
- alumina
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002808 molecular sieve Substances 0.000 claims abstract description 77
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 61
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- 159000000013 aluminium salts Chemical class 0.000 claims abstract description 6
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 239000003610 charcoal Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000002283 diesel fuel Substances 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000009833 condensation Methods 0.000 abstract description 7
- 230000005494 condensation Effects 0.000 abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 6
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010457 zeolite Substances 0.000 abstract description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009415 formwork Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 230000003319 supportive effect Effects 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- 239000003921 oil Substances 0.000 description 12
- 239000000499 gel Substances 0.000 description 10
- 238000005336 cracking Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 235000010210 aluminium Nutrition 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- -1 carbonium ion Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 230000036299 sexual function Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of modified form H-G hydrocracking catalyst and preparation method thereof, catalyst raw material includes following components and percentage by weight：4~25% molecular sieve, 10~65% γ Al2O3, 15~70% amorphous silica-alumina, 9~40% binding agent and 7~35% reactive metal oxides；Specific surface area of catalyst is 220~450m2/ g, total pore volume is 0.30~0.73cm3/g.The present invention adds the molecular sieve of not Template removal during molecular sieve and alumina composite material is prepared, in mixed liquor, the NH4 that aluminium salt is generated with ammoniacal liquor reaction+Alkali Na+ with balance molecule sieve skeleton frame negative electrical charge is swapped, in roasting process, while by organic formwork agent and NH in molecular sieve4 +Removing; so as to the ammonium that zeolite molecular sieve is completed in composite material is prepared is exchanged and Template removal; exchanged without individually carrying out Template removal and ammonium to molecular sieve; template has support and protective effect to molecular sieve pore passage structure; this catalyst can be on the premise of ensureing diesel oil in high yield; the condensation point of diesel oil distillate is significantly reduced, the Cetane number of diesel oil is improved.
Description
Technical field
The present invention relates to catalyst, in particular to a kind of modified form H-G hydrocracking catalyst and preparation method thereof.
Background technology
In recent years, with China's rapid development of economy, the demand rapid growth of various oil products, and the demand of diesel oil is always
Occupy first of various oil products.Restricted by the original feature of processing and work flow, the yield of diesel oil, especially low freezing point diesel fuel
Yield, limited by distillate condensation point, this turns into " bottleneck " problem of the northern oil refining enterprise's economic benefit of restriction.Therefore,
The quality and yield of low freezing point diesel fuel are improved, is still the problem for enjoying enterprises pay attention to meet the market demand.This is also to hydrogenation
Cracking technology proposes requirement higher, and catalyst plays the role of a nucleus in hydrocracking reaction, the pass of hydrocracking technology
Key is the development and improvement of catalyst.
The conventional preparation method of hydrocracking catalyst mainly has infusion process, coprecipitation, kneading method etc., wherein kneading method
Preparation technology it is most simple, the requirement to technique and catalyst dispensing is not high, but because its preparation process is more extensive, catalyst
The poor dispersion of middle each component, part metals hydrogenation sites are capped, it is impossible to preferably play its activity, usually add
Hydrogen performance requirement is not that catalyst very high is used；Coprecipitation technology of preparing preparation process is the most complicated, but in catalyst
Very well, the matching relationship between each component is good for the decentralization of each component, and hydrogenation and cracking activity center are uniformly divided in the catalyst
Cloth, makes catalyst hydrogenation have synergy higher with cracking activity center；Infusion process is to prepare hydrocracking catalyst most
Extensive application method, needs to prepare shape first, and mechanical strength, specific surface and acidity etc. meet the load of catalyst performance requirement
Body, then carries out carried metal component by saturation or supersaturated dipping method, and metal component is enriched in catalyst, makes catalysis
Agent has mechanical strength higher, gives full play to its Hydrogenation.
However, hydrocracking catalyst obtained in existing method, is all simple mechanical mixture, catalyst between its component
It is offspring that middle each component is easily reunited so that active component dispersiveness is poor, and the catalyst of preparation is difficult to play optimality
Can, but also there is preparation flow complexity, the problem of high cost.Such as：US4738767 discloses a kind of hydrocracking catalyst,
Its main acidic components is amorphous silica-alumina, and the preparation method of the amorphous silica-alumina used by carrier is by aluminum precipitation to Silica hydrogel
In, the specific surface area and pore volume that this results in sial are all smaller, acid measure low and skewness the features such as, catalyst activity is not
It is high.CN1351121A discloses a kind of hydrocracking catalyst containing modified beta molecular sieve and amorphous silicon aluminium and preparation method thereof,
Modified beta molecular sieve is that the molecular sieve pulp after synthesis is directly carried out into ammonium exchange in the method, be then calcined de- ammonium, acid treatment and
Hydro-thermal process obtains modified beta molecular sieve, because a large amount of non-framework aluminums are trapped in molecular sieve pore passage, have impact on modified molecular screen
Acid and its diffusion, finally have impact on the yield and property of diesel product.CN1393521A discloses a kind of middle oil type and adds
Hydrogen Cracking catalyst and preparation method thereof, catalyst used carrier is the compound molecule of amorphous silica-alumina, aluminum oxide and Y and β
Sieve, wherein composite molecular screen will be after mixing with modified Y molecular sieve after beta-molecular sieve original powder burning-off template, then carry out ammonium exchange
Process and obtain, the catalysis activity of the catalyst is not high, the product quality of the intermediate oil of boat coal and diesel oil is general, need further
Improve.
The content of the invention
Present invention aim to provide a kind of modified form H-G hydrocracking catalyst and preparation method thereof, the catalysis
Agent can be on the premise of diesel yield be ensured, it will be apparent that reduce the condensation point of diesel oil distillate, improves the Cetane number of diesel oil.
To achieve the above object, the technical solution adopted by the present invention is：A kind of modified form H-G hydrocracking catalyst, institute
Stating catalyst raw material includes following components and its percentage by weight：4~25% molecular sieve, 10~65% γ-Al2O3, 15~
70% amorphous silica-alumina, 9~40% binding agent and 7~35% reactive metal oxides；The specific surface of the catalyst
Product is 220~450m2/ g, total pore volume is 0.30~0.73cm3/g。
Further, the catalyst raw material includes following components and its percentage by weight：2~4% molecular sieve, 20~
34% γ-Al2O3, 20~35% amorphous silica-alumina, 13~40% binding agent and 18~29% active metal are aoxidized
Thing；The specific surface area of the catalyst is 342~361m2/ g, total pore volume is 0.50~0.57cm3/g；The catalyst is in post
Shape, length is 3~8mm.
Further, the molecular sieve is beta-molecular sieve, Y type molecular sieve, MOR molecular sieves, ZSM-5 molecular sieve, ZSM-22 point
Son sieve and ZSM-23 molecular screen in one or more.
Further, the active metal in the reactive metal oxides is one or more in W, Mo, Ni and Co.
Further, the beta-molecular sieve specific surface area is 450~750m2/ g, total pore volume is 0.3~0.5cm3/g。
Further, the amorphous silica-alumina pore volume is 0.5~1.0cm3/ g, specific surface area is 300~500m2/g。
Further, containing the small porous aluminum oxide that mass percent is 10~40% in the binding agent, remaining is acid；Institute
Aperture aluminum oxide pore volume is stated for 0.3~0.5cm3/ g, specific surface area is 200~350m2/ g is described sour with the small porous aluminum oxide
Mass ratio is 0.1~0.5.
A kind of preparation method of above-mentioned modified form H-G hydrocracking catalyst carrier, comprises the following steps：
1) hydrothermal synthesis method prepares molecular sieve：Tetraethylammonium bromide solution, NaOH, silicon source and water are mixed and stirred for
To settled solution, silicon source is subsequently adding, continues stirring and obtain silica-alumina gel；Then silica-alumina gel is carried out into crystallization, through washing and
Dried process, obtains molecular sieve；
2) molecular sieve and γ-Al are prepared2O3Composite：By step 1) molecular sieve that obtains adds the mixed of aluminium salt and ammoniacal liquor
Precipitated in conjunction solution, fully take slurries after precipitation is evaporated successively, dries and calcination process, obtains molecular sieve and aluminum oxide
Composite；
3) catalyst is prepared：By step 2) gained molecular sieve and alumina composite material, amorphous silicon al binder and work
Property metal oxide mixed by the material rate, roll successively, be molded, dry and activate, you can it is described hydrogenation split
Change catalyst.
Further, the step 1) in, silicon source, silicon source, NaOH, tetraethylammonium bromide solution and water rub by dispensing
You compare SiO2∶Al2O3∶Na2O: tetraethylammonium bromide: H2O adds for 50~70: 1: 5~8: 15~20: 1000~1200 ratio
Enter.
Further, the step 2) in, aluminium salt is the aluminium chloride of 0.5~3.0mol/L, the concentration of ammoniacal liquor for 0.5~
4mol/L。
Further, the step 2) in, molecular sieve is 0.4~0.9cm with the pore volume of alumina composite material3/ g, than
Surface area is 350~500m2/g。
Further, the step 1) in, molecular sieve is beta-molecular sieve, and crystallization temperature is 135~145 DEG C；It is washed to washing
Liquid pH is 6.5~7.5；Drying temperature is 90~110 DEG C, and drying time is 22~26h.
Further, the step 2) in, in precipitation process, temperature is 60~80 DEG C, and pH is 3~7；Drying temperature is 90
~120 DEG C, drying time is 2~3 hours；Sintering temperature is 300~600 DEG C, and roasting time is 2~8 hours.
Further, the step 3) in, drying temperature is 100~120 DEG C, and drying time is 18~22 hours, activation
Temperature is 450~600 DEG C, and soak time is 4~6 hours.
Further, the step 2) in, the concentration of ammoniacal liquor is 1.0~2.0mol/L.
Further, the step 1) in, silicon source is the one kind or several in boehmite, aluminum sulfate and sodium metaaluminate
Kind；Silicon source is one or more in white carbon, Ludox and waterglass.
Compared with prior art, the present invention has advantages below：
First, the invention provides a kind of H-G hydrocracking method for preparing catalyst, preparing γ-Al2O3Inorganic aluminum
The zeolite molecular sieve of not Template removal is added in salting liquid, through precipitation, is dried and is calcined, obtain molecular sieve and γ-Al2O3Answer
Condensation material, wherein, in mixed liquor, the NH4 that aluminium salt is generated with ammoniacal liquor reaction+Alkali Na+ with balance molecule sieve skeleton frame negative electrical charge enters
Row is exchanged, in roasting process, while by organic formwork agent and NH in molecular sieve4 +Removing, the template of removing is mainly to be filled out
Fill the TEA of duct inside and balance molecule sieve skeleton frame negative electrical charge+, and NH4 +Then with NH3Form be removed, obtain H- beta molecules
Sieve, so as to the ammonium that zeolite molecular sieve is completed in composite material is prepared is exchanged and Template removal, without individually to zeolite
Molecular sieve carries out Template removal and ammonium is exchanged, and not only simplifies preparation technology, and template has branch to zeolite cavity structure
Support and protective effect, zeolite molecular sieve maintain good pore passage structure.
Second, being mixed composite with other materials according to catalyst preparation ratio, roll, be molded, dry and
Activation obtains catalyst, and because molecular sieve decentralization is high in catalyst carrier of the present invention, carrier has more uniform acidic site, oxygen
It is even closer that change aluminium is contacted with molecular sieve, is conducive to reactant and product molecule fast between acid centre and cracking center
Speed transfer, Cracking Component and hydrogenation component have obtained optimization and have coordinated, the hydrocracking catalyst intermediate oil prepared using it
Selectivity is high.
Third, the hydrogenation sites of catalyst of the present invention and the matching of cracking activity center are more rationally, with more preferable
Intermediate oil selectivity, can high-output qulified midbarrel oil product, and catalysis activity is very high, can ensure diesel oil in high yield
Under the premise of, it will be apparent that the condensation point of diesel oil distillate is reduced, the Cetane number of diesel oil is improved, is suitable for processing the hydrogenation of vacuum distillate
Cracking produces the catalytic process of fine-quality diesel oil.
Fourth, carrier specific surface area of the present invention is big, pore passage structure is broad unimpeded, can provide more Mass Transfer Apparatus meetings, expands
Dissipate speed it is high, reactant molecule can be rapidly entered inside carrier duct, realize reaction molecular acid centre and hydrogenation in
Fast transfer between the heart, product can be escaped quickly, it is to avoid the generation of secondary side reaction.Meanwhile, present invention optimization
Matching between hydrogenating function and acid function, forms strong hydrogenation function and is combined with middle acid or weak acid sexual function, carbonium ion
Saturation more can be hydrogenated with hydrogenation sites is carried out to isomerization direction, reduces the secondary cracking of pyrolysis product.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, is easy to more clearly understand the present invention,
But they do not constitute to the present invention and limit.
In following examples, specific surface area and pore volume use low temperature N2Physisorphtion is determined, silica alumina ratio useization
Method is determined, and meleic acid amount, B acid amount and L acid amounts are determined using Pyridine adsorption IR spectra method, and molecular sieve relative crystallinity is used
XRD method is determined.
The preparation of hydrocracking catalyst is carried out as follows in following examples：
Molecular sieve pulp after crystallization is directly filtered, washed, being dried, and Template removal treatment is not carried out after drying, its
SiO2/Al2O3(mol ratio) is 20~60；Aluminum salt solution and alkali precipitation agent are mixed, the molecular sieve of above-mentioned not Template removal is added
In entering mixed solution, stirring, temperature control at 60~80 DEG C, pH value control 3~7, in being carried out under 50~90 DEG C of temperature conditionss
Be calcined for precipitation by evaporation, 100 DEG C of dryings, and sintering temperature is 300~600 DEG C, and roasting time is 2~6 hours, is divided
Son sieve and alumina composite material；According to catalyst mixed proportion, by molecular sieve and alumina composite material, amorphous silica-alumina,
(small porous aluminum oxide pore volume is 0.3~0.5cm in the binding agent for reactive metal oxides and binding agent3/ g, specific surface area is 200
~350m2/ g, acid and alumina ratio are 0.1~0.5 in binding agent, and acid is HNO3Or H3PO4) mixed, in edge runner
Roll 20~60 minutes, into column, carrier lengths are 3~8nm to extrusion, then by strip carrier in 100~120 DEG C of dryings 10
~20 hours, it is calcined 4~6 hours at 450~600 DEG C, obtains hydrocracking catalyst.
Embodiment 1
Weigh 201.3g tetraethylammonium bromides (98wt%, technical grade), 27.39g NaOH, 7.2g boehmites
(70wt%, technical grade), 870g water is mixed and stirred for settled solution, then be stirred continuously it is lower to solution in add 180g white
Carbon black (98wt%, technical grade), and continue stirring to obtain uniform silica-alumina gel；By silica-alumina gel in 145 DEG C of dynamic crystallizations 7
My god, beta-molecular sieve is obtained after being dried through separation of solid and liquid and washing, numbering is B1, and the main character of the beta-molecular sieve is shown in Table 1.
By in 3000ml liquor alumini chloridis (concentration is 1.5mol/L) addition 5000ml beakers, 19g B1 molecular sieves (are done
Base 99%) add mixed liquor in, 70 DEG C of constant temperature, be continuously added 2mol/L ammoniacal liquor until pH value be 4, at 85 DEG C evaporate, will
In being dried 3 hours at 100 DEG C, roasting obtains molecular sieve and alumina composite material in 4 hours to the white solid of sucking-off at 500 DEG C
273.7g (butt 93%), conversion ratio is 72.5%, and numbering is C1.
By 183.7g (butt 93%) C1, amorphous silica-alumina 172.7g (butt 88%), MoO395.5g (99.1wt%),
Ni(NO3)2·6H2O (NiO, 26.6wt%) 106.7g, binding agent 240g (butt 30%) are mixed, and are carried out in edge runner
Roll 40 minutes, it is toothpaste-squeezable shape to roll, extruded moulding, support shapes are column, length is 3~8nm, then by strip carrier in
120 DEG C of dryings 20 hours, are calcined 5~6 hours at 550 DEG C, obtain catalyst H-1, and property is shown in Table 2.
Embodiment 2
Weigh 201.3g tetraethylammonium bromides (98wt%, technical grade), 27.39g NaOH, 7.2g boehmites
(70wt%, technical grade), 870g water is mixed and stirred for settled solution, then be stirred continuously it is lower to solution in add 180g white
Carbon black (98wt%, technical grade), and continue stirring to obtain uniform silica-alumina gel；By silica-alumina gel in 145 DEG C of dynamic crystallizations 7
My god, beta-molecular sieve is obtained after being dried through separation of solid and liquid and washing, numbering is B1, and the main character of the beta-molecular sieve is shown in Table 1.
By in 3000ml liquor alumini chloridis (concentration is 1.5mol/L) addition 5000ml beakers, 28g B1 molecular sieves (are done
Base 99%) add mixed liquor in, 70 DEG C of constant temperature, be continuously added 2mol/L ammoniacal liquor until pH value be 4, at 85 DEG C evaporate, will
In being dried 3 hours at 100 DEG C, roasting obtains molecular sieve and alumina composite material in 4 hours to the white solid of sucking-off at 500 DEG C
276.2g (butt 93%), conversion ratio is 73%, and numbering is C2.
By 225.1g (butt 93%) C2, amorphous silica-alumina 126.8g (butt 88%), MoO3It is 114.3g
(99.1wt%), Ni (NO3)2·6H2O (NiO, 26.6wt%) is mixed for 167.4g, binding agent 240g (butt 30%),
Carry out rolling 40 minutes in edge runner, it is toothpaste-squeezable shape to roll, extruded moulding, support shapes are column, length is 3~8nm,
Again by strip carrier in 120 DEG C of dryings 20 hours, it is calcined 5~6 hours at 550 DEG C, obtains catalyst H-2, property is shown in Table 2.
Embodiment 3
Weigh 185.3g tetraethylammonium bromides (98wt%, technical grade), 22.65g NaOH, 10.3g boehmites
(70wt%, technical grade), 870g water is mixed and stirred for settled solution, then be stirred continuously it is lower to solution in add 180g white
Carbon black (technical grade), and continue stirring to obtain uniform silica-alumina gel；By silica-alumina gel in 145 DEG C of dynamic crystallizations 7 days, through solid
Beta-molecular sieve is obtained after liquid is separated and washing is dried, numbering is B2, and the main character of the beta-molecular sieve is shown in Table 1.
By 3000ml liquor alumini chloridis (concentration is 1.5mol/L) add 5000ml beakers in, by 60.5g B2 molecular sieves
(butt 99%) is added in mixed liquor, 70 DEG C of constant temperature, is continuously added the ammoniacal liquor of 2mol/L up to pH value is 4, in evaporation at 85 DEG C,
In being dried 3 hours at 100 DEG C, roasting obtains molecular sieve and alumina composite material in 4 hours to the white solid that will be suctioned out at 500 DEG C
296.4g (butt 93%), conversion ratio is 78.4%, and numbering is C3.
By 145.7g (butt 93%) C3, amorphous silica-alumina 210.7g (butt 88%), MoO3It is 104.5g
(99.1wt%), Ni (NO3)2·6H2O (NiO, 26.6wt%) is mixed for 113.7g, binding agent 240g (butt 30%),
Carry out rolling 40 minutes in edge runner, it is toothpaste-squeezable shape to roll, extruded moulding, support shapes are column, length is 3~8nm,
Again by strip carrier in 120 DEG C of dryings 20 hours, it is calcined 5~6 hours at 550 DEG C, obtains catalyst H-3, property is shown in Table 2.
Embodiment 4
Weigh 185.3g tetraethylammonium bromides (98wt%, technical grade), 22.65g NaOH, 10.3g boehmites
(70wt%, technical grade), 870g water is mixed and stirred for settled solution, then be stirred continuously it is lower to solution in add 180g white
Carbon black (technical grade), and continue stirring to obtain uniform silica-alumina gel；By silica-alumina gel in 145 DEG C of dynamic crystallizations 7 days, through solid
Beta-molecular sieve is obtained after liquid is separated and washing is dried, numbering is B2, and the main character of the beta-molecular sieve is shown in Table 1.
By 3000ml liquor alumini chloridis (concentration is 1.5mol/L) add 5000ml beakers in, by 34.3g B2 molecular sieves
(butt 99%) is added in mixed liquor, 70 DEG C of constant temperature, is continuously added the ammoniacal liquor of 2mol/L up to pH value is 4, in evaporation at 85 DEG C,
In being dried 3 hours at 100 DEG C, roasting obtains molecular sieve and alumina composite material in 4 hours to the white solid that will be suctioned out at 500 DEG C
285.3g (butt 93%), conversion ratio is 75.6%, and numbering is C4.
By 196.4g (butt 93%) C4, amorphous silica-alumina 159.6g (butt 88%), MoO3It is 108.5g
(99.1wt%), Ni (NO3)2·6H2O (NiO, 26.6wt%) is mixed for 183.7g, binding agent 240g (butt 30%),
Carry out rolling 40 minutes in edge runner, it is toothpaste-squeezable shape to roll, extruded moulding, support shapes are column, length is 3~8nm,
Again by strip carrier in 120 DEG C of dryings 20 hours, it is calcined 5~6 hours at 550 DEG C, obtains catalyst H-4, property is shown in Table 2.
Embodiment 3 and the gained catalyst H-3 and H-4 of embodiment 4 are evaluated on fixed bed hydrogenation experimental provision, is commented
Valency condition is：Reaction stagnation pressure is 10MPa, and hydrogen to oil volume ratio is 1000, volume space velocity 1.0h-1, it is using vacuum distillate (VGO)
Feedstock oil, the raw material oil nature is shown in Table 3.Catalyst H-3 and H-4 is evaluated under identical process conditions, evaluation result
4 are shown in Table, as can be seen from Table 4, under identical process conditions, catalyst midbarrel grease separation prepared by carrier of the present invention
Selecting property is good, it is ensured that on the premise of diesel yield, it will be apparent that reduce the condensation point of diesel oil distillate, improves the Cetane number of diesel oil.
Table 1
| Molecular sieve | B1 | B2 |
| Silica alumina ratio (Si/Al) | 31.5 | 22.6 |
| Relative crystallinity, % | 96 | 105 |
| Specific surface, m2/g | 624 | 643 |
| Total pore volume, ml/g | 0.32 | 0.35 |
| Meleic acid amount, mmol/g | 0.29 | 0.31 |
| B acid/L acid | 0.56 | 0.48 |
Table 2
Table 3
| Feedstock oil | Vacuum distillate |
| Density (20 DEG C), kg/m3 | 912.3 |
| Boiling range, DEG C | |
| IBP/10% | 315/403 |
| 30%/50% | 442/461 |
| 70%/90% | 495/526 |
| 95%/EBP | 532/544 |
| Condensation point, DEG C | 32 |
| Nitrogen, μ g/g | 1568 |
| Carbon, wt% | 84.53 |
| Hydrogen, wt% | 11.72 |
| Carbon residue, wt% | 0.32 |
| BMCI values | 43 |
Table 4
Claims (16)
1. a kind of modified form H-G hydrocracking catalyst, it is characterised in that：The catalyst raw material include following components and its
Percentage by weight：4~25% molecular sieve, 10~65% γ-Al2O3, 15~70% amorphous silica-alumina, 9~40% it is viscous
Knot agent and 7~35% reactive metal oxides；The specific surface area of the catalyst is 220~450m2/ g, total pore volume is 0.30
~0.73cm3/g。
2. modified form H-G hydrocracking catalyst according to claim 1, it is characterised in that：The catalyst raw material includes
Following components and its percentage by weight：2~4% molecular sieve, 20~34% γ-Al2O3, 20~35% amorphous silica-alumina,
13~40% binding agent and 18~29% reactive metal oxides；The specific surface area of the catalyst is 342~361m2/
G, total pore volume is 0.50~0.57cm3/g；The catalyst is in the form of a column, and length is 3~8mm.
3. modified form H-G hydrocracking catalyst according to claim 1 or claim 2, it is characterised in that：The molecular sieve is β points
One kind or several in sub- sieve, Y type molecular sieve, MOR molecular sieves, ZSM-5 molecular sieve, ZSM-22 molecular sieves and ZSM-23 molecular screen
Kind.
4. modified form H-G hydrocracking catalyst according to claim 1 or claim 2, it is characterised in that：The active metal oxygen
Active metal in compound is one or more in W, Mo, Ni and Co.
5. modified form H-G hydrocracking catalyst according to claim 3, it is characterised in that：The beta-molecular sieve specific surface
Product is 450~750m2/ g, total pore volume is 0.3~0.5cm3/g。
6. modified form H-G hydrocracking catalyst according to claim 1 or claim 2, it is characterised in that：The amorphous silica-alumina
Pore volume is 0.5~1.0cm3/ g, specific surface area is 300~500m2/g。
7. modified form H-G hydrocracking catalyst according to claim 1 or claim 2, it is characterised in that：Contain in the binding agent
Mass percent is 10~40% small porous aluminum oxide, and remaining is acid；The aperture aluminum oxide pore volume is 0.3~0.5cm3/ g,
Specific surface area is 200~350m2/ g, it is described it is sour be 0.1~0.5 with the aperture quality of alumina ratio.
8. the preparation method of modified form H-G hydrocracking catalyst carrier described in a kind of claim 1, it is characterised in that：Including
Following steps：
1) hydrothermal synthesis method prepares molecular sieve：Tetraethylammonium bromide solution, NaOH, silicon source and water are mixed and stirred for clear
Clear solution, is subsequently adding silicon source, continues stirring and obtains silica-alumina gel；Then silica-alumina gel is carried out into crystallization, through washing and drying
Treatment, obtains molecular sieve；
2) molecular sieve and γ-Al are prepared2O3Composite：By step 1) molecular sieve that obtains adds the mixing of aluminium salt and ammoniacal liquor molten
Precipitated in liquid, fully take slurries after precipitation is evaporated successively, dries and calcination process, obtains molecular sieve and alumina composite
Material；
3) catalyst is prepared：By step 2) gained molecular sieve and alumina composite material, amorphous silicon al binder and activity gold
Category oxide is mixed by the material rate, is rolled successively, is molded, drying and activating, you can is obtained described being hydrocracked and is urged
Agent.
9. the preparation method of modified form H-G hydrocracking catalyst according to claim 8, it is characterised in that：The step
1) in, silicon source, silicon source, NaOH, tetraethylammonium bromide solution and water press dispensing mol ratio SiO2∶Al2O3∶Na2O: tetraethyl
Ammonium bromide: H2O is added for 50~70: 1: 5~8: 15~20: 1000~1200 ratio.
10. the preparation method of modified form H-G hydrocracking catalyst according to claim 8, it is characterised in that：The step
It is rapid 2) in, aluminium salt is the aluminium chloride of 0.5~3.0mol/L, and the concentration of ammoniacal liquor is 0.5~4mol/L.
11. according to claim 8 or 9 or 10 modified form H-G hydrocracking catalyst carrier preparation method, its feature
It is：The step 2) in, molecular sieve is 0.4~0.9cm with the pore volume of alumina composite material3/ g, specific surface area be 350~
500m2/g。
12. according to claim 8 or 9 or 10 modified form H-G hydrocracking catalyst carrier preparation method, its feature
It is：The step 1) in, molecular sieve is beta-molecular sieve, and crystallization temperature is 135~145 DEG C；Be washed to cleaning solution pH for 6.5~
7.5；Drying temperature is 90~110 DEG C, and drying time is 22~26h.
13. according to claim 8 or 9 or 10 modified form H-G hydrocracking catalyst carrier preparation method, its feature
It is：The step 2) in, in precipitation process, temperature is 60~80 DEG C, and pH is 3~7；Drying temperature is 90~120 DEG C, is dried
Time is 2~3 hours；Sintering temperature is 300~600 DEG C, and roasting time is 2~8 hours.
14. according to claim 8 or 9 or 10 modified form H-G hydrocracking catalyst carrier preparation method, its feature
It is：The step 3) in, drying temperature be 100~120 DEG C, drying time be 18~22 hours, activation temperature be 450~
600 DEG C, soak time is 4~6 hours.
15. according to claim 8 or 9 or 10 modified form H-G hydrocracking catalyst carrier preparation method, its feature
It is：The step 2) in, the concentration of ammoniacal liquor is 1.0~2.0mol/L.
16. according to claim 8 or 9 or 10 modified form H-G hydrocracking catalyst carrier preparation method, its feature
It is：The step 1) in, silicon source is one or more in boehmite, aluminum sulfate and sodium metaaluminate；Silicon source is hard charcoal
One or more in black, Ludox and waterglass.
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| WO2018192516A1 (en) * | 2017-04-21 | 2018-10-25 | 武汉凯迪工程技术研究总院有限公司 | Improved diesel hydrocracking catalyst carrier and method for preparing same |
| WO2018192517A1 (en) * | 2017-04-21 | 2018-10-25 | 武汉凯迪工程技术研究总院有限公司 | Improved diesel hydrocracking catalyst and method for preparing same |
| CN116060103A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Modified beta molecular sieve and preparation method and application thereof |
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| CN116020537B (en) * | 2021-10-25 | 2024-06-07 | 中国石油化工股份有限公司 | Catalyst for producing lubricating oil base oil, and preparation method and application thereof |
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